Quaternary ammonium salts of chloromethylated silicon compounds

ABSTRACT

QUATERNARY AMMONIUM SALTS OF CHLOROMETHYLATE SILANES OR SILOXANES WHICH CONTAINS AT LEAST ONE   (CL-R3&#34;N+CH2-AR-(R$N)   RADICAL DIRECTLY LINKED TO A SILICON ATOM WHEREIN AR IS AN ARYLENE RADICAL, WHEREIN R&#34;2N TAKEN COLLECTIVELY IS A TERTIARY AMINE RADICAL AND WHEREIN THE COMPOUNDS ARE USEFUL IN CONVENTIONAL SILICON APPLICATON SUCH AS ANTISTATIC AGENTS, WETTING AGENTS LUBRICANTS, HYDRAULIC FLUIDS COATING RESINS, ELASTOMERS AND CATIONIC SURFACTANTS.

United States Patent Office 3,661,963 Patented May 9, 1972 3,661,963QUATERNARY AMMONIUM SALTS F CHLORO- METHYLATED SILICON COMPOUNDS EnricoJ. Pepe, Amawalk, and Bernard Kanner, West Nyack, N.Y., assignors toUnion Carbide Corporation, New York, N .Y.

No Drawing. Continuation-impart of abandoned application Ser. No.423,414, Dec. 31, 1964. This application Mar. 3, 1969, Ser. No. 803,973

Int. Cl. C071? 7/10, 7/18 US. Cl. 260-448.2 N 18 Claims ABSTRACT OF THEDISCLOSURE Quaternary ammonium salts of chloromethylated silanes orsiloxanes which contain at least one radical directly linked to asilicon atom wherein Ar is an arylene radical, wherein R" N takencollectively is a tertiary amine radical and wherein the compounds areuseful in conventional silicon applications such as antistatic agents,wetting agents, lubricants, hydraulic fluids, coating resins, elastomersand cationic surfactants.

[cl-Wm CH2-Ar(R)n] wherein Ar is an arylene radical, R is an alkyleneradical, R is a monovalent hydrocarbon radical, X is a halogen radical,preferably fluorine or chlorine, or OR wherein R is as defined above, RN taken collectively represents a tertiary amine which can be either aheterocyclic tertiary amine wherein the amino nitrogen is present in aring structure with carbon atoms, or a tertiary amine wherein the aminonitrogen represented by N is bonded to three monovalent organic radicalsrepresented by R", n is an integer having a value of from 0 to 1, a isan integer having a value of from 1 to 3, and b is an integer having avalue of from 0 to 2, provided, however, that the sum of a+b does notexceed 3. Preferably, a has a value of 1 and the sum of d+b does notexceed 2, as silanes having only a single hydrolyzable group attached tosilicon are not useful in the preparation of polysiloxanes except asend-blocking units.

The arylene radicals represented by Ar in Formula 1 above can be eithermonocyclic, bicyclic, or a fused ring, and can be unsubstituted orsubstituted with substituents which are inert under the reactionconditions employed in the invention. Usually such radicals have from 6to about 18 carbon atoms. Illustrative of such radicals are o-phenylene,m-phenylene, p-phenylene, tolylene, xylylene, nitrophenylene,t-butylphenylene, naphthylene, anthrylene, methylnaphthylene,diphenylene, and the like. Preferably Ar represents a phenylene radical,most preferably p-phenylene.

The alkylene radicals represented by R in Formula 1 above can be eitherstraight or branched chain radicals,

and can be unsubstittued or substituted with substituents which areinert under the reaction conditions employed in the invention. Usuallysuch radicals have from 1 to about 12 carbon atoms, preferably from 1 toabout 8 carbon atoms. Illustrative of such radicals are methylene,ethylene, propylene, isopropylene, butylene, tertiarybutylene,pentylene, 2-ethylhexylene, dodecylene, and the like.

The monovalent hydrocarbon radicals represented by R in Formula 1 cancontain from 1 to 20 carbon atoms, and can be unsubstituted orsubstituted with substituents which are inert under the reactionconditions employed in the invention. Such radicals include straight andbranched chain alkyl radicals such as methyl, ethyl, npropyl, isopropyl,n-butyl, isobutyl, n-pentyl, n-hexyl, 2- ethylhexyl, n-decyl, n-dodecyl,n-tetradecyl, n-hexadecyl, n-octadecyl, eicosyl, and the like; alkenylradicals such as vinyl, allyl, and the like; cycloaliphatic radicalssuch as cyclopentyl, cyclohexyl, and the like; aryl radicals such asphenyl, nitrophenyl, naphthyl, p-phenylphenyl, and the like; aralkylradicals such as benzyl, ,fi-phenylethyl, and the like; and alkarylradicals such as p-methylphenyl, p-cyclohexylphenyl, a-methylnaphthyl,and the like. Preferably R is an alkyl radical containing from 1 to 18carbon atoms and most preferably from 1 to 8 carbon atoms.

The heterocyclic tertiary amines represented by R" N in Formula 1 abovehave a ring structure containing both nitrogen and carbon atoms in thering, and optionally other atoms, such as oxygen. The nitrogen presentin the ring makes up the tertiary amino group of the amine. The ring ofthe amine can be unsubstituted or substituted, provided, however, thatthe substituted or unsubstituted amine is inert under the reactionconditions employed in the invention except for the ability of the amineto form a quaternary compound. Such amines usually contain up to about18 carbon atoms, preferably from 3 to about 13 carbon atoms.Illustrative of such heterocyclic tertiary amines are acridine,benzoxazole, isoquinoline, isoxazole, oxazine, oxazoline, oxazole,phenanthridine, pseudoindole, pyridine, 3-cyanopyridine,2-ethylpyridine, 2- vinylpyridine, quinoline, quinuclidine, thiazine,thiazoline, thiazole, and the like. The most preferred quaternarycompounds are pyridine and quinoline heterocyclic tertiary amines.

When R" N of Formula 1 above represents a tertiary amine wherein theamino nitrogen represented by N is bonded to three monovalent organicradicals represented by R, the monovalent organic radicals representedby R" contain carbon and hydrogen atoms, and optionally other atoms,such as oxygen, provided, however, that the resulting amine is inertunder the reaction conditions employed in the invention except for theability of the amine to form a quaternary compound. Such radicalsinclude straight and branched chain alkyl radicals such as methyl,ethyl, methacryloxyethyl, acryloxyethyl, n-propyl, isopropyl, n-butyl,isobutyl, n-pentyl, n-hexyl, n-heptyl, 2-ethylhexyl, n-decyl, n-dodecyl,n-tetradecyl, n-hexadecyl, noctadecyl, and the like; alkenyl radicalssuch as vinyl, allyl, and the like; cycloaliphatic radicals such ascyclopentyl, cyclohexyl, and the like; aryl radicals such as phenyl,nitrophenyl, naphthyl, p-phenylphenyl, and the like; aralkyl radicalssuch as benzyl, B-phenylethyl, and the like; alkaryl radicals such asp-methylphenyl, p-cyclohexylphenyl, a-methylnaphthyl, and the like.Preferably each R" is a monovalent hydrocarbon radical having from 1 to18 carbon atoms and most preferably an alkyl radical from 1 to 8 carbonatoms.

The chloromethylarylsilane quaternary ammonium salts and thechloromethylaralkylsilane quaternary ammonium salts of the instantinvention are produced by reacting a tertiary amine of formula R" N asdescribed above with a chloromethylarylsilane or achloromethylaralkylsilane represented by the formula wherein Ar, R, R,X, n, a and b are as above defined.

Silanes corresponding to Formula 2 above wherein X is halogen or OR',and R is an alkyl radical, can be produced by reacting a suitablearylsilane or aralkylsilane with chloromethyl methyl ether and thionylchloride, optionally in the presence of a catalytic amount of zincchloride, at temperatures of from about 35 C. to about 120 C., to effectchloromethylation of the aryl radical of the silane, as disclosed incopending application Ser. No. 422,495, filed concurrently herewith, nowUS. Pat. No. 3,413,329, which disclosure is incorporated herein byreference.

When X is a halogen other than fluorine in Formula 2 above, it ispossible to readily replace such halogen with OR groups, wherein R is amonovalent hydrocarbon radical as defined above with reference toFormula 2, by reacting the silane with a compound of the formula whereinR is as above defined. Although the reaction wherein the halogen atomsare replaced with OR groups is spontaneous and proceeds without benefitof a catalyst even at room temperature, a small amount of an acidacceptor such as triethylamine can be employed to effect the removal ofthe last traces of halogen. Preferably, a mole percent excess of ROH isemployed,

When X is fluorine in Formula 2 above, it is possible to replace suchfluorine atoms with OR groups, wherein R is as defined above, by thecatalyzed redistribution of silicone-fluorine and silicon-hydrocabyloxybonds as described in copending application Ser. No. 313,442, filed Oct.3, 1963, now US. Pat. No. 3,374,247, which disclosure is incorporatedherein by reference. In accordance with that technique, a fluorosilaneis heated in contact with a silicon compound (preferably a silane)containing at least one, and preferably at least three, hydrocarbyloxygroups directly attached to silicon, and with a redistribution catalystsuch as tetrabutyltitanate, aluminum trichloride, tin dichloride,zironium tetraethoxide, and the like, to effect redistribution of thesilicon-fluorine and siliconhydrocarbyloxy bonds.

Thus, by followng the procedures outlined above, it is possible toproduce all the silanes of Formula 2 above which are useful in theinstant invention.

Quaternary ammonium salts of chloromethylarylsilanes andchloromethylaralkylsilanes are produced according to the instantinvention by reacting a silane of Formula 2 above with a tertiary amineof formula R N as described above. While it is preferable to use anexcess of the amine, for example an excess of from about 5 mole percentto about 100 mole percent stoichiometric equivalent of chloromethylarylof chloromethylaralkyl group of the silane to be quaternized, anequivalent amount of the amine can also be employed.

While, in general, temperatures of from about C. to about 250 C. can beemployed in preparing the desired quaternary ammonium salts of theinstant invention, the preferred temperature is dependent upon thebasicity and steric configuration of the amine employed. Temperatures offrom about 80 C. to about 150 C. are preferred for amines having lowbasicity (such as pyridine, quinoline, and the like), and temperaturesof from about 150 C. to about 250 C. are preferred for amines havingbulky organic groups (such as triallylamine, trioctadecylamine, and thelike).

Atmospheric pressure is usually employed in effecting reaction as amatter of convenience. However, if desired,

4 subatmospheric or superatmospheric pressures can also be employed.

The chloromethylarylsilane quaternary ammonium salts and thechloromethylaralkylsilane quaternary ammonium salts produced inaccordance with the instant invention can be hydrolyzed and condensed inthe conventional manner, either alone or together with otherhydrolyzable silanes, to produce siloxanes containing at least one unitdepicted by the formula wherein R" N, Ar, R, R', n, a, and b are asabove defined. When the silanes of the instant invention arecohydrolyzed and condensed with other hydrolyzable silanes, thesiloxanes produced can also contain at least one unit depicted by theformula wherein R is a monovalent hydrocarbon radical as defined abovewith reference to Formula 1, and m is an integer having a value of from1 to 3. Such siloxane units are produced by the hydrolysis of silanes ofthe formula wherein R and m are as above defined, and X is halogen orOR.

Thus, the chloromethylarylsilane quaternary ammonium salts and thechloromethylaralkylsilane quaternary ammonium salts of the instantinvention can be employed to prepare siloxanes composed of units of thestructure depicted by Formula 4, or siloxanes composed of one or moreunits depicted by Formula 4 and one or more units depicted by Formula 5.Such siloxanes can contain up to about 5 percent by weight ofhydrolyzable groups which have not been hydrolyzed.

If desired, silanes of Formula 2 can be hydrolyzed and condensed eitheralone, or together with silanes of Formula 6, to produce siloxanes whichcan then be treated with an amine of formula R N, above defined withreference to Formula 1, to produce the quaternary ammonium siloxanesdescribed above. The proportions of ingredients and reaction conditionsemployed in producing quaternary ammonium salts ofchloromethylarylsilanes and chloromethylaralkylsilanes can also beemployed when a siloxane is treated with a tertiary amine to produce aquaternary ammonium siloxane.

While no solvent is necessary in effecting quaternization of silanes andsiloxanes according to the instant invention, in some instances solventssuch as ethanol, methanol, benzene, toluene, and the like, can be usedto advantage, as for example, when only partial quaternization of apolysiloxane is desired.

The quaternary ammonium silanes and siloxanes pro duced in accordancewith the instant invention can be purified by reprecipitation in inertsolvent combinations of, for example, hexane-toluene, acetone-hexane,ethanoltoluene, methanol-isopropyl ether, and the like. However, certainof the above solvents, such as ethanol, methanol, and acetone, as wellas moisture, should be avoided when groups reactive therewith arepresent, e.g., silicon-bonded chlorine radicals.

The silanes of the instant invention can be used in binder sizing ofglass as an anti-static agent to lower the migration of binder in thewinding operation; they can also be used to control electricalconductivity of mineral filled polymers by treating the filler with thesilane and bonding the hydrolyzate of silane to the filler surface or bypremixing the silane in the polymer prior to incorporation of thefiller; they can also be used to change the wettability of the filler inpolymers and polymer containing emulsions. In addition the silanes canbe used to prepare the siloxane polymers disclosed herein. The siloxanesof the instant invention are useful as cationic surfacts and also inconventional siloxane applications, including uses as lubricants,hydraulic fluids, coating resins for metals and fibers, and elastomers.The siloxane polymers of this invention are also useful as lubricantadditives in the treatment of inorganic oxide surfaces, such as glass,glass fibers and other siliceous substrates to impart lubricity and toimprove their processing characteristics.

The following examples are illustrative of the present invention and arenot to be regarded as limitative. It is to be understood that all parts,percentages and proportions referred to herein are by weight unlessotherwise indicated.

EXAMPLE 1 To a 6-inch test tube were charged 11.7 grams (0.05 mole) ofbeta-(chloromethylphenyl)ethylmethyldifiuorosilane and 5.6 grams (0.055mole) of triethylamine, causing an immediate reaction. The tube wassealed with a glass stopper and heated at a temperature of 90 C. for 1hour. At the end of this time, the mixture was heated to 150 C. andmaintained at this temperature for 2 minutes. Following this, themixture was stripped under vacuum, leaving 10 grams of a salt-likeresidue of Cl Et N+CH CH CH SiMeF This represented a yield of 60 percentby weight. The product was purified by extraction with anhydrous ethylether. The purified product was a white, powdery, hydroscopic,water-soluble salt which had a neutralization equivalent of 168(theoretical=171).

Analysis.-Calculated for C H SiNF Cl (percent): C, 57.2; H, 8.4; Si,8.4; N, 4.2; F, 11.3; C1, 10.6. Found (percent) C, 56.0; H, 8.5; Si,7.0; N, 4.3; F, 8.4; Cl,

EXAMPLE 2 To a 6-inch test tube were charged 13.4 grams (0.05 mole) ofchloromethylneophyltrifluorosilane and 5.6 grams (0.055 mole) oftriethylamine, causing an immediate reaction. The tube was sealed andheated at a temperature of 90 C. for 1 hour. At the end of this time,the mixture was heated to 150 C. and maintained at this temperature for2 minutes under vacuum. The residue, a dark salt weighing 9.4 grams,represented a 50 percent by Of c1 Et3N CH2C(CH3) CHgSiFg. The productwas purified by precipitation from acetone with diethyl ether. Thepurified product was a white, watersoluble salt.

Analysis.Calculated for C H SiNF Cl (percent): C1, 9.6; F, 15.5; Si,7.6. Found (percent): Cl, 11.8; F, 12.5; Si, 7.7.

EXAMPLE 3 A mixture of beta-(chloromethylphenyl)ethyltriethoxysilane anda 50 percent molar excess of triallylamine was dissolved in 2 volumes ofethanol, and the solution was heated in a sealed pressure vessel at atemperature of 250 C. for 4 hours. The solution was then stripped undervacuum, and a dark brown residue of was recovered. The product wassoluble in water, and a mixture acetone and water, but was insoluble inpentane, ethyl acetate, and isopropyl ether.

EXAMPLE 4 To a 250-milli1iter distillation flask were charged 33 grams(0.1 mole) of beta-(chloromethylphenyl)propyltriethoxysilane, 17 grams(0.11 mole of dimethylaminoethylmethacrylate, and 0.5 gram of Ionol (ananti-oxidant). The mixture was heated at a temperature of 150 C. for 15minutes, extracted with five loo-milliliter portions of hexane, anddissolved in 200 milliters of toluene. Hexane was then added to thesolution to precipitate 6 The product was purified by precipitation fromtoluene with diethyl ether to give 40.6 grams of a dry white powder,representing a yield of 84 percent by weight. The purified product had amelting point of -92 C., a bromine number of 32 (theoretical=32.7), wassoluble in hot toluene, water, ethanol and acetone, and insoluble inhexane and diethyl ether.

Analysis.Calculated for C H SiO NCl (percent): C, 59.1; H, 8.7; Si, 5.8;CI, 7.3; N, 2.9. Found (percent): C, 56.9; H, 8.5; Si, 5.7; Cl, 7.8; N,2.5.

EXAMPLE 5 To a 200-milliliter flask were charged 16.5 grams (0.05 mole)of beta-(chloromethylphenyl)propyltriethoxysilane and 7.9 grams (0.10mole) of pyridine. The mixture was refluxed for 45 minutes and strippedof volatiles. The residue was dissolved in toluene, and diethyl etherwas then added to the solution to precipitate in quantitative yields.The product was a light yellow resin which had a softening point of 50C., was soluble in water and acetone, and insoluble in diethyl ether.

Analysis.Calculated for C H SiO NCl (percent): C, 61.5; H, 7.9; Si, 6.8;C1, 8.6; N, 3.4. Found (percent): C, 59.3; H, 7.4; Si, 7.1; Cl, 10.2; N,2.0.

EXAMPLE 6 wherein Me represents a methyl radical and 5 represents aphenyl radical. The siloxane had surface active properties and wasuseful as a surfactant.

When an excess of pyridine was reacted with the methylsiloxane fluid ina similar manner in a sealed tube at C. for 48 minutes, a pyridiniumquaternary derivative was obtained. This product also had surface activeproperties and was useful as a surfactant and may be illustrated by theformula MeSiO I: CHM C CH H CHaSlMBO 5H5N+Cl wherein Me and 4: are thesame as defined above.

EXAMPLE 7 Other quaternary ammonium compounds can be prepared byfollowing the procedure outlined in Examples 1 to 6 of reacting one moleof the silane reactant with a slight molar excess of amine and replacingthe above amine reactants with other amines such as, trimethylamine,methyldiethylamine, methyldioctadecylamine, phenyldimethylamine,phenyldiethylamine, tripropylamine, trioctadecylamine, trioctylamine,2ethylpyridine, quinoline, and the like and/or replacing the silanereactant with other silanes such as,

beta- (chlo romethylphenyl) propylmethyldichloro silane,ch10romethylneophyltrichlorosilane,

beta- (chlo romethylphenyl) propyltrichloro silane,

beta- (chloromethylphenyl propyltrifluorosilane,

beta- (chloromethylphenyl ethyltrifluorosila'ne,

beta- (chloromethylphenyl octyltrifluorosilane,

beta- (chloromethylphenyl) propylmethyldifluorosilane,

7 betachloromethylphenyl propyloctadecyldifiuorosilane,beta-(chloromethylphenyl)propyltrimethoxysilane, beta-(chloromethylphenyl propylmethyldiethoxysilane,beta-(chloromethylphenyl)propyloctadecyldiethoxysilane and the like.

EXAMPLE 8 Into a 100 ml., 3-necked flask, outfitted with mechanicalstirrer, thermometer, water condenser and heating mantle was charged11.2 grams (0.03 mole) of C H Si(OMe) 5.4 grams, mole of ofapproximately equal parts and 18 grams of iospropano]. The stirredmixture was heated to reflux, whereupon dropwise addition of 1.35 gramsof 0.1 N HCl was made over about 1 minute. The mixture was heated atreflux of /2 hour, followed by a 1-liter per minute sparge, at reflux,with gaseous trimethyamine until quaternization was completed. Reactionwas judged complete when a clear 1 wt. percent solution of the totalmixture in water was obtained, usually after 15 minutes. Vacuumstripping at 100 C. to 1 mm. of mercury pressure produced a clear,colorless homogeneous silicone copolymer characterized by the formula 1ss7 3 2) 0.6 a 2 2 4 3 2) 0.4( 0.4 having the indicated mole fraction ofcationic groups.

Cationic silicone copolymers containing 20, 10, 5 and 2.5 mole percentof quaternary ammonium grouping were also prepared. Physical propertiesand elemental analyses for the complete series are summarized in TableI, below.

TABLE I wherein Ar is an arylene radical; R is an alkylene radical; R isa monovalent hydrocarbon radical; X is a radical selected from the groupconsisting of halogen and OR wherein R is as defined above; R" N takencollectively represents a tertiary amine wherein theamino nitrogenrepresented by N is bonded to three monovalent radicals selected fromthe group consisting of methacryloxyethyl, acryloxyethyl and monovalenthydrocarbon radicals; n has a value of from 0 to 1; a is an integerhaving a value of from 1 to 3; and b has a value of from 0 to 2,provided, however, that the sum of (a+b) does not exceed 3; and (B)siloxanes consisting of at least one siloxy unit represented by theformula wherein Ar, R, R, R" N, n, a, b and (a-l-b) are the same asdefined above; and at least one siloxy unit represented by the formulawherein R is the same as defined above and m is an integer from 1 to 3.

2. A quaternary ammonium salt of a silane as defined in clami 1, whereinAr is an arylene radical having from 6 to 18 carbon atoms; R is analkylene radical having from 1 to 12 carbon atoms; R is a monovalenthydrocarbon radical having from 1 to 20 carbon atoms; and R N takencollectively is a tertiary amine wherein the amino nitrogen representedby N is bonded to three [Cationic silicone copolymers (x+y=100 molepercent)] Analysis, percent Solubility Calculated Found Composition (1wt.-percent (mole-percent 01 y) M.P., C. in H1O) Si N 01 Si N Cl 44-45Soluble 9.6 1 92 4. 86 1.66 45-46 Disperses 9.5 0 96 2 43 Added to 60 C.water as 6 wt.-percent solution insopropanol.

The siloxane copolymers are especially useful as glass fiber productionlubricants and can be used alone or as additives to conventional formingsize compositions.

Other copolymers can be prepared by employing approximately the samemole ratio of ingredients as outlined above, but replacing theoctadecyltrimethoxysilane with other silanes such asmethyltrimethoxysilane, ethyltrimethoxysilane, octadecyltriethoxysilane,eicosyltrimethoxysilane, and the like; and/or replacing(chloromethylphenyl)ethyltrimethoxysilane with other silanes such as(chloromethylphenyl)propyltrimethoxysilane,chloromethylneophyltrimethoxysilane, and the like; and/or replacingtrimethylamine with other amines such as, triethylamine, triallylamine,dimethylaminoethylmethacrylate, pyridine, methyldiethylamine,methyldioctadecylamine, phenyldimethylamine, phenyldiethylamine,tripropylamine, trioctadecylamine, trioctylamine, 2-ethylpyridine,quinoline, and the like Various modifications and variations of thisinvention will be obvious to a worker skilled in the art and it isunderstood that such modifications and variations are to be includedwithin the purview of this application and the spirit and scope of theappended claims.

What is claimed is:

1. A quaternary ammonium salt selected from the group consisting of (A)silanes represented by the formula monovalent radicals selected from thegroup consisting of methacryloxyethyl and monovalent hydrocarbonradicals having from 1 to 18 carbon atoms; a is an integer having avalue of 1 and the sum of (a+b) does not exceed 2.

3. A quaternary ammonium salt of a siloxane as defined in claim 1wherein Ar is an arylene radical having from 6 to 18 carbon atoms; R isan alkylene radical having from 1 to 12 carbon atoms; R is a monovalenthydrocarbon radical having from 1 to 20 carbon atoms; and R N takencollectively is a tertiary amine wherein the amino nitrogen representedby N is bonded to three monovalent radicals selected from the groupconsisting of methacryloxyethyl and monovalent hydrocarbon radicalshaving from 1 to 18 carbon atoms.

4. A quaternary ammonium salt of a silane as defined in claim 1, whereinX is fluorine and the sum of (a-l-b) does not exceed 2.

5. A quaternary ammonium salt of a silane as defined in claim 1, whereinX is chlorine and the sum of (a+b) does not exceed 2.

6. A quaternary ammonium salt as defined in claim 2 wherein X isfluorine.

7. A quaternary ammonium salt as defined in claim 2 wherein X ischlorine.

8. A quaternary ammonium salt as defined in claim 2, wherein Ar isphenylene; -R is an alkylene radical having from 1 to 8 carbon atoms; Ris an alkyl radical having from 1 to 8 carbon atoms; R" N takencollectively is a tertiary amine wherein the amino nitrogen representedby N is bonded to three monovalent alkyl radicals having from 1 to 8carbon atoms; and n is an integer having a value of 1.

9. A quaternary ammonium salt as defined in claim 8, wherein X isfluorine.

10. A quaternary ammonium salt as defined in claim 8, wherein X ischlorine.

11. A quaternary ammonium salt as defined in claim 8, wherein X is ORand R represents an alkyl radical having from 1 to 8 carbon atoms.

12. A quaternary ammonium salt as defined in claim 3, wherein Ar isphenylene; R is an alkylene radical having from 1 to 8 carbon atoms; R'is an alkyl radical having from 1 to 18 carbon atoms; R" N takencollectively is a tertiary amine wherein the amino nitrogen representedby N is bonded to three monovalent alkyl radicals having from 1 to 8carbon atoms; and n is an integer having a value of 1.

13. A quaternary ammonium salt as defined in claim 12, wherein R is analkyl radical selected from the group consisting of methyl and octadecylradicals.

14. A quaternary ammonium silane salt represented by the formula whereinis a phenylene radical.

15. A quaternary ammonium silane salt represented by the formula whereinis a phenylene radical.

16. A quaternary ammonium silane salt represented by the formula CI"CHC(CH )COOCH CH N+(CH CH C(CH )HCH Si(OC H wherein is a phenyleneradical.

17. A quaternary ammonium silane salt represented by the formula whereinis a phenylene radical.

18. A quaternary ammonium siloxane salt comprising siloxy units of theformula wherein is a phenylene radical and the mole ratio of x to yranges from about 60 to about 99 mole percent of siloxy units of FormulaI above to about 1 to about 40 mole percent of siloxy units of FormulaII above.

References Cited UNITED STATES PATENTS 2,972,598 2/1961 Morehouse260448.2 N X 3,362,933 1/1968 Culpepper 260-448.2 N X 3,402,191 9/ 1968Morehouse 260-4482 N 3,471,541 10/ 1969 Morehouse 260-4482 N X DELBERTE. GANTZ, Primary Examiner P. F. SHAVER, Assistant Examiner US. Cl. X.R.

25249.6, 77; 260-46.5 G, 448.2 B, 448.2 Q, 448.8 R, 283 SC, 289 R, 290S, 297 S UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PatentNo. 3 66] 963 Issue Date Mav 9. 1972 Inventor) Enrico J. Pepe et a1.

It is certified that error appeere in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

In claim 18, lir 1e 5, the far left bend portion of formula (11) shownas "Cl should read --Cl y[--.

Signed and sealed this 29th day 'of August 1972.

(SEAL) Attest;"

EDWARD M,-FLETCHER ./;J R- I ROBERT GOTTSCHALK Attesting OfficerCommissioner of Patents

